JPH03220310A - Yarn of poly-4-methyl-1-pentene resin - Google Patents

Abstract

PURPOSE:To obtain the title yarn maintaining heat aging resistance for a long period of time, not changing color, by subjecting a composition prepared by blending poly-methyl-pentene resin with a specific compound and dipropionic ester as a stabilizer to melt spinning. CONSTITUTION:A composition comprising (A) poly 4-methyl-1-pentene resin, (B) a triazine-based compound shown by formula I [X<1> to X<3> are group shown by formula II (A<1> is alkylene; R<1> is 1-10C alkyl adjoining to CH; R<2> to R<4> are n or 1-10C alkyl)] or a benzene-based compound shown by formula III (R<5> to R<7> are H or alkyl; X<4> to X<6> are X<1>) and (C) a dipropionic ester or a pentaerithritol tetraalkylthiopropionic ester is subjected to the objective yarn. 1,3,5-Tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate is preferably used as the component B and dilauryl-3,3'-thiodilauryl propionate is preferable as the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a poly-4-methyl-1-pentene resin fiber that can maintain heat aging resistance for a long period of time and does not discolor.

[Conventional technology]

Fibers made of poly-4-methyl-1-pentene resin have a good texture and texture, and are therefore being considered as a raw material for fabrics for futons, sportswear, etc.

Various stabilizers are added to such poly-4-methyl-1-pentene resin fibers in order to improve properties such as heat aging resistance.
- When methyl-1-pentene resin fibers are washed repeatedly, the added stabilizer decomposes and gradually dissolves into water, causing a problem in that heat aging resistance is significantly reduced.

Furthermore, poly-4-methyl-1-pentene resin fibers are easily colored (pink or yellow) by exposure to nitrogen oxide in the air, so if they are exposed to car exhaust gas or dried using an oil stove after washing, etc. There is a problem that the color changes easily.

[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned problems.
Poly 4 that can maintain heat aging resistance for a long time and does not change color.
- To provide a methyl-1-pentene resin fiber.

[Means to solve the problem]

The present invention is the following poly-4-methyl-1-pentene resin fiber.

(1) (A) Poly 4-methyl-1-pentene resin, (
B) (i) Triazine compound 3 represented by the following general formula [I] (in the formula, x1 to x3 are each an alkylene group ', and R1 is a carbon number 1 to 1 adjacent to the hydroxyl group)
The alkyl group of 0 and R2-R4 each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. x1 to X3 may be the same or different. ) or (i) a benzene compound represented by the following general formula [■] (wherein R5-R7 are each a hydrogen atom or a carbon number 1
The above alkyl groups, x4 to x6 are respective alkylene groups, R8 is an alkyl group having 1 to 10 carbon atoms adjacent to the hydroxyl group, and R9 to R11 are each a hydrogen atom or a carbon number of 1 to 10.
Indicates the alkyl group of lO. x4 to X' may be the same or different. ) and (C) a poly-4-methyl-1-pentene resin fiber obtained by melt-spinning a composition consisting of a dipropionate ester or a pentaerythritol tetraalkylthiopropionate ester.

Poly 4-methyl-1-pentene resin used in the present invention (
A) is a homopolymer of 4-methyl-1-pentene, and a copolymer of 4-methyl-1-pentene and other α-olefins, mainly composed of 4-methyl-1-pentene. Poly 4-methyl-1-pentene resins such as copolymers can be used. Other α-olefins copolymerized with 4-methyl-1-pentene include:

For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 3-
Examples include α-olefins such as ethyl-1-hexene.

The triazine compound 1) represented by the general formula [I] used in the present invention is a stable compound that does not decompose even if it comes into contact with water such as tap water for a long period of time and/or repeatedly. Such triazine compounds (i) include, for example, 1,3.5-)-lis(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3.5-tris( 3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,
3.5-)-Lis(3-methyl-5-t-butyl-4
-hydroxybenzyl) isocyanurate and the like. Among these are 1,3.5-)-Lis(
2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanate, 1,3.5-tris(3
, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate is preferred, and these may be used alone or in combination of two or more.

The benzene compound (i) represented by the general formula (I[) used in the present invention is a stable compound that does not decompose even if it comes into contact with water such as tap water for a long period of time and/or repeatedly. It is. As such a benzene compound (i), for example, 1,3,5-trimethyl-2,4,6-
Tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3.5-)-liethyl-2,4
．． 6-tris(3,5-di-t-butyl-4'-hydroxybenzyl)benzene, 1,3.5-trimethyl-
2,4,6-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)benzene, 1,3.5-
Trimethyl-2,4,6-tris(3-methyl-5-t
-Butyl-4-hydroxybenzyl)benzene, among others, 1,3゜5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4
-hydroxybenzyl)benzene is preferred, and these may be used alone or in combination of two or more.

Examples of the dipropionate esters used in the present invention include dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, simiristyl-3,3'-thiodipropionate, etc. can be given. Among these, dilauryl-3,3'-
Thiodipropionate is preferred.

Examples of the pentaerythritol tetraalkylthiopropionate used in the present invention include pentaerythritol tetralaurylthiopropionate,
Examples include pentaerythritol tetrabutylthiopropionate, pentaerythritol tetraoctylthiopropionate, and pentaerythritol tetrastearylthiopropionate. Among these, pentaerythritol tetralauryl thiopropionate is preferred.

In the present invention, poly-4-meth, thiru-1-pentene resin (A
), by adding a combination of component (B) of the triazine compound (+) or the benzene compound (i), and component (C) of the dipropionate or pentaerythritol tetraalkylthiopropionate. , a poly-4-methyl-1-pentene resin fiber that can maintain heat aging resistance for a long period of time and does not change color can be obtained. These properties are not available with other common stabilizer formulations.

Each component of the poly-4-methyl-1-pentene resin composition (hereinafter referred to as raw material poly-4-methyl-1-pentene resin composition) before spinning the poly-4-methyl-1-pentene resin fiber of the present invention. The blending ratio is usually 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight of component (B), and 100 parts by weight of poly4-methyl-1-pentene resin (A). It is preferred that the components are usually 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight.

The raw material poly-4-methyl-1-pentene resin composition in the present invention has component (A), component (B), and component (C) as essential components, but in addition to these components, peroxide compounds, metal soap, etc. can be blended.

Examples of peroxide compounds include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxides such as 1,1-bis(t-butylperoxy)cyclohexane and 2,2-bis(t-butylperoxy)octane; Oxyketals; t-butyl hydroperoxide, cumene hydroperoxide, 2
．． Hydroperoxides such as 5-dimethylhexane-2,5-dihydroxyperoxide, 1,1,3,3-tetramethylbutylhydroperoxide; di-t-butylperoxide, 2,5-dimethyl-2, 5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5
-Dialkyl peroxides such as di(t-butylperoxy)hexyne-3; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; t-butylperoxyacetate, t-butylperoxybenzoate, 2,5- Examples include peroxy esters such as dimethyl-2,5-di(benzoylperoxy)hexane.

The peroxide compound is preferably blended in an amount of usually 2 to 0.01 parts by weight, preferably 0.5 to 0.05 parts by weight, per 100 parts by weight of the poly-4-methyl-1-pentene resin (A).

Examples of the metal soap include alkali metal salts of saturated or unsaturated carboxylic acids having 12 to 40 carbon atoms.

Examples include alkaline earth metal salts and other metal salts. Moreover, the above-mentioned saturated or unsaturated carboxylic acid having 12 to 40 carbon atoms may have a substituent such as a hydroxyl group. Specific examples of saturated or unsaturated carboxylic acids having 12 to 40 carbon atoms include stearic acid, oleic acid, lauric acid, capric acid, arachidonic acid, palmitic acid, behenic acid, 12-hydroxystearic acid, and montanic acid. of higher fatty acids.

Metals that react with these higher fatty acids to form salts include alkaline earth metals such as magnesium, calcium and barium; alkali metals such as sodium, potassium and lithium; cadmium; zinc; and lead. can.

Metal soap is poly 4-methyl-1-pentene resin (A)
It is preferred that the amount is usually 0.01 to 3 parts by weight, preferably 0.03 to 1 part by weight per 100 parts by weight.

Furthermore, the raw material poly-4-methyl-1-pentene resin composition in the present invention contains various compounding agents 1, such as nucleating agents, plasticizers, and heat-resistant stabilizers, which can be blended with the polyolefin within a range that does not impair the purpose of the present invention. , a weathering stabilizer, a lubricant, an antistatic agent, an antifogging agent, an inorganic or organic filler, a dye, a pigment, etc. may be added.

Known methods can be used to obtain the raw material poly-4-methyl-1-pentene resin composition in the present invention. For example, a method of mixing the above-mentioned components in a V-blender, a ribbon blender, a Henschel mixer, a tumbler blender, or A method of mixing in the blender and then granulating with an extruder, or a single-screw extruder, a double-screw extruder, or a kneader.
Examples include a method of melt-kneading with a Banbury mixer or the like, followed by granulation or pulverization.

The poly-4-methyl-1-pentene resin fiber of the present invention can be obtained by spinning the raw material poly-4-methyl-1-pentene resin composition by a known method. A method in which a polymer fluid in which a methyl-1-pentene resin composition is heated and dissolved is extruded from a spinning die and the fluid is cooled and solidified as it is, a method in which the fluid is passed through a solidifying liquid and solidified, or a method in which the fluid is dissolved in an appropriate solvent Examples of the method include extruding a solution of the raw material poly-4-methyl-1-pentene resin composition from a spinning die and vaporizing the solvent with hot air.

The poly-4-methyl-1-pentene resin fiber thus obtained does not lose its heat aging resistance even if it is washed repeatedly. This is due to the synergistic effect of the combination of component (B) of triazine compound (i) or benzene compound (i) added as a stabilizer, and component (C) of dipropionate or pentaerythritol tetraalkylthiopropionate. It is presumed that this is due to the fact that

Furthermore, a triazine compound (i
), benzene compound (i), dipropionate ester, and pentaerythritol tetraalkylthiopropionate ester, none of which react with NOx gas or the amine compound contained in the oil agent used during the spinning process. Even if the poly-4-methyl-1-pentene resin fiber of the invention is washed and dried with a gas burner, it will not change color.

Therefore, the poly-4-methyl-1-pentene resin fiber of the present invention can be used in futon fabrics, sportswear, diapers, industrial filters, quilted coats, quilted jumpers, futon bags, wrapping cloths, and carrier bags.

Wiping cloths, simple clothing, medical gowns.

It can be used as a raw material for surgical coverings, etc.

[Effects of the Invention] According to the present invention, a specific stabilizer is added to the poly-4-methyl-1-pentene resin in combination, so that the poly-4-methyl-1-pentene resin can maintain heat aging resistance for a long period of time and does not discolor. Methyl-1-pentene resin fibers are obtained.

〔Example〕

Examples of the present invention will be described below.

Example I MFR (260°C, 5kg) 5 g/10+*i
n 4-methyl-1-pentene polymer powder (hereinafter referred to as PN
0.10 parts by weight of dilauryl thiodipropionate (hereinafter abbreviated as DLT),
1,3.5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate (hereinafter referred to as GRI
After weighing 0.20 parts by weight of calcium stearate (hereinafter abbreviated as SCA) and 0.03 parts by weight of calcium stearate (hereinafter abbreviated as SCA), they were mixed at high speed for 1 minute using a Henschel mixer (soQ).

This mixture was then passed through a twin-screw extruder (manufactured by Hoso Tekko Co., Ltd.).
PCM45, resin temperature 290"C) Kneading, granulation and MF
R (260° C.) 180 g/10+*in PMP pellets were obtained.

The PNP pellets thus obtained were put into a Mello 511-diameter extruder at a temperature of 300° C., heated and melted, and spun as follows.

0.3mmφ with 1mm pitch on the nozzle provided in the die
Using an extruder with 1,000 orifices arranged in a row, the molten polymer was discharged from the orifices at a rate of 0.2 g/min.
It was discharged through an orifice. Heated steam at 280°C is injected from the slits on both sides of this orifice, the molten polymer is clarified, and the fiber group is collected on a cooling drum that rotates once. It was made into a web. The die temperature is 310℃, and the heating steam pressure is 2
．． It was 0 kg/aIG. The average fiber diameter of the obtained web was 0.4 μm.

The heat aging resistance and pink discoloration of the thus obtained web after washing were measured by the following methods. The results are shown in Table 1.

Measurement method (1) Heat aging resistance test after washing (JIS L1096
) Washing machine (Yurendori, product name, manufactured by Sanyo Electric Co., Ltd.)
50 g of detergent (ZABU, trade name, manufactured by Kao Corporation) is placed in it, and 50°C warm water is poured into it. The resulting web was placed inside and stirred vigorously for 20 minutes, followed by washing with water for 5 minutes. After repeating this operation 30 times, the web is taken out and dried at room temperature. Thereafter, the sample is placed in an air oven at 160° C., and the time until appearance deterioration occurs is visually determined.

(2) Pink change test The obtained web was hung directly above a kerosene stove, and the time until the appearance of the web turned pink was visually observed.

Example 2 1.3.5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (hereinafter referred to as TTA) was used instead of GRI used in Example 1. The same procedure as in Example 1 was carried out except that (omitted) was used. The results are shown in Table 1.

Example 3 Instead of DLT used in Example 1, pentaerythritol tetralauryl thiopropionate (hereinafter referred to as
The same procedure as in Example 1 was conducted except that PET (abbreviated as PET) was used. The results are shown in Table 1.

Comparative Example 1 Instead of GRI used in Example 1, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane (
The same procedure as in Example 1 was conducted except that TNM (hereinafter abbreviated as TNM) was used. The results are shown in Table 1.

Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Example 1, except that tetraethylthiuram disulfide (hereinafter abbreviated as TET) was used as a stabilizer instead of DLT used in Example 1. The results are shown in Table 1.

Claims (1)

[Claims] (1) (A) Poly 4-methyl-1-pentene resin, (B
) (i) Triazine compound represented by the following general formula [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, X^2 to X^3 are respectively ▲mathematical formula, chemical formula, There is a table etc. ▼ is shown here. Here, A
^1 is an alkylene group having 1 or more carbon atoms, R^1 is an alkyl group having 1 to 10 carbon atoms adjacent to a hydroxyl group, R^2 to R^4
each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X^1 to X^3 may be the same or different. ) or (ii) A benzene compound represented by the following general formula [II]▲There are mathematical formulas, chemical formulas, tables, etc.▼...[III] (In the formula, R^5 to R^7 are each hydrogen atom or carbon The alkyl groups of number 1 or more, X^4 to X^5, each represent ▲There are numerical formulas, chemical formulas, tables, etc.▼.Here, A^2
is an alkylene group having 1 or more carbon atoms, R^8 is an alkyl group having 1 to 10 carbon atoms adjacent to a hydroxyl group, R^9 to R^1^1
each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X^4 to X^6 may be the same or different. ) and (C) a poly-4-methyl-1-pentene resin fiber obtained by melt-spinning a composition consisting of a dipropionate ester or a pentaerythritol tetraalkylthiopropionate ester.